CN113235290B - Preparation method of ether bond-linked polybasic carboxyl modified regenerated cellulose - Google Patents
Preparation method of ether bond-linked polybasic carboxyl modified regenerated cellulose Download PDFInfo
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- CN113235290B CN113235290B CN202110583204.2A CN202110583204A CN113235290B CN 113235290 B CN113235290 B CN 113235290B CN 202110583204 A CN202110583204 A CN 202110583204A CN 113235290 B CN113235290 B CN 113235290B
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- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 73
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000006266 etherification reaction Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical class CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000007127 saponification reaction Methods 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 125000004185 ester group Chemical group 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims description 48
- 239000000835 fiber Substances 0.000 claims description 45
- 239000000047 product Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000009987 spinning Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920002678 cellulose Polymers 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000012190 activator Substances 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000010041 electrostatic spinning Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- 150000002500 ions Chemical class 0.000 abstract description 15
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 14
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229920001410 Microfiber Polymers 0.000 description 10
- 239000003658 microfiber Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- FNJVDWXUKLTFFL-UHFFFAOYSA-N diethyl 2-bromopropanedioate Chemical group CCOC(=O)C(Br)C(=O)OCC FNJVDWXUKLTFFL-UHFFFAOYSA-N 0.000 description 4
- 238000006011 modification reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000002121 nanofiber Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 description 2
- FEIQOTQVKWCPLT-UHFFFAOYSA-L disodium;2-bromopropanedioate Chemical compound [Na+].[Na+].[O-]C(=O)C(Br)C([O-])=O FEIQOTQVKWCPLT-UHFFFAOYSA-L 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- WLWCQKMQYZFTDR-UHFFFAOYSA-N diethyl 2-chloropropanedioate Chemical compound CCOC(=O)C(Cl)C(=O)OCC WLWCQKMQYZFTDR-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
- D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
- D06M2101/08—Esters or ethers of cellulose
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a preparation method of ether bond connected multi-carboxyl modified regenerated cellulose, which comprises the steps of firstly changing ester groups of cellulose acetate into hydroxyl groups through saponification reaction, then adding halogenated diethyl malonate to perform alkali catalysis etherification grafting reaction to enable halogen and the hydroxyl groups to perform grafting reaction and simultaneously hydrolyze ester groups of the halogenated diethyl malonate into carboxyl groups, and finally soaking in dilute acid solution until carboxylate is completely converted into the carboxyl groups to obtain ether bond connected multi-carboxyl modified regenerated cellulose products. According to the invention, a polybasic carboxyl group is introduced on the surface of regenerated cellulose through an in-situ etherification reaction, and the polybasic carboxyl modifier is firmly bonded and connected with the regenerated cellulose through a covalent bond-ether bond, so that carboxyl is not easy to fall off, and a cellulose acetate product is not dissolved and swelled with the increase of the introduced amount of carboxyl, can tolerate a water environment with high pH value, has higher stability and adsorption capacity in the environment, and can be used for removing heavy metal ions.
Description
Technical Field
The invention belongs to the field of regenerated cellulose modification, and particularly relates to a preparation method of ether bond-linked polybasic carboxyl modified regenerated cellulose.
Background
With the concern of people on the ecological environment, various technical means about water pollution treatment are rapidly developed, and the removal of heavy metal ions in water bodies has been a research focus all the time, wherein the removal of the heavy metal ions by an adsorption technology is a simple, effective and environment-friendly method. Researches show that the polymer adsorbent has the advantages of high adsorption amount, good reutilization property and the like in the aspect of treating heavy metal polluted wastewater, and the biodegradable material is the first choice of the environment-friendly polymer adsorbent. The cellulose, especially the cellulose nano-fiber, has outstanding performance in removing heavy metal ions.
It should be noted that pure cellulose has a weak removal ability due to its numerous hydroxyl groups, and in order to improve its adsorption ability, it is generally required to perform a functionalization treatment to introduce a functional group applicable as a ligand, such as a carboxyl group, a sulfonic acid group, an amine group, an amide group, a thiol group, and the like. Document Zhang Kai, Li Zongjie, Deng Nanping, et al, Tree-like cellulose nanofibranes modified by strategy acid for latent metal ion (Cu) 2 + )removal[J]Cellulose,2019,26(2): 945-958) adopts a citric acid modification method to introduce a polybasic carboxyl group into Cellulose, but the reaction is carried out under high temperature and high pressure conditions, and the citric acid and the Cellulose are connected through an ester bond, so that the Cellulose has poor resistance to higher acid and alkaline environments. Literature "Ricardo Chagas, Martin Gericke, Ricardo B.Ferreira, et al.Synthesis and catalysis of dicarbonylymethyl cell [ J]Cellulose,2020,27:1965-1974, uses sodium bromomalonate for carboxylation modification of Cellulose powder, but sodium bromomalonate is a non-commercial product, and the water solubility of Cellulose powder increases with the degree of substitution of hydroxyl groups in Cellulose, and thus, the Cellulose powder cannot be used as a heavy metal ion adsorbent. Therefore, a new route and a new method for preparing the heavy metal ion adsorbent, which have tolerance to a high-pH water environment, mild reaction conditions, low cost and simple process, are urgently needed to be developed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing ether bond connected multi-carboxyl modified regenerated cellulose.
The technical scheme for solving the technical problem is to provide a preparation method of ether bond connected polybasic carboxyl modified regenerated cellulose, which is characterized by comprising the following steps:
step 2, mixing the regenerated cellulose product obtained in the step 1, a solvent and an alkali activator, activating the regenerated cellulose, adding halogenated diethyl malonate to perform an alkali-catalyzed etherification grafting reaction to enable halogen and hydroxyl to perform a grafting reaction and ester groups of the halogenated diethyl malonate to be hydrolyzed into carboxyl groups, and obtaining an initial product;
and 3, washing the primary product obtained in the step 2 to remove unreacted substances and micromolecular byproducts, thereby completing the purification of the primary product, and then soaking the primary product into a dilute acid solution until the carboxylate is completely converted into carboxyl, thereby obtaining the ether bond-linked polybasic carboxyl modified regenerated cellulose product.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, a polybasic carboxyl group is introduced on the surface of regenerated cellulose through an in-situ etherification reaction, and the polybasic carboxyl modifier is firmly bonded and connected with the regenerated cellulose through a covalent bond-ether bond, so that carboxyl is not easy to fall off, and a cellulose acetate product is not dissolved and swelled with the increase of the introduced amount of carboxyl, can tolerate a water environment with high pH value, has higher stability and adsorption capacity in the environment, and can be used for removing heavy metal ions.
(2) When the cellulose acetate product adopts the nano-micron fiber membrane, the high specific surface area and the porosity of the nano-micron fiber membrane endow the material with high adsorption performance and rapid substance transmission and diffusion in the fiber membrane, and the etherification reaction does not damage the fiber structure.
(3) The method has the advantages of simple process, mild reaction, low post processing cost, easy operation, good use adaptability and easy industrial popularization.
(4) The halogenated diethyl malonate used as the modifying reagent is a commercial pharmaceutical chemical synthesis intermediate and can be directly purchased and applied.
Drawings
FIG. 1 is a reaction scheme of the process of the present invention;
FIG. 2 is an SEM image of ether linkage multi-carboxyl modified regenerated cellulose nano-micro fiber membrane prepared in example 1 of the invention;
FIG. 3 is the IR spectrum of ether linkage multi-carboxyl modified regenerated cellulose nano-micro fiber membrane prepared in example 1 of the present invention;
FIG. 4 is an SEM image of an ether-linked poly-carboxyl-modified regenerated cellulose nano-micro fiber membrane prepared in example 2 of the invention;
FIG. 5 is the IR spectrum of ether linkage multi-carboxyl modified regenerated cellulose nano-micro fiber membrane prepared in example 2 of the present invention;
FIG. 6 is an SEM image of ether linkage multi-carboxyl modified regenerated cellulose nano-micro fiber membrane prepared in example 3 of the invention;
FIG. 7 is an IR spectrum of an ether-linked polycarboxy-modified regenerated cellulose nanofiber membrane prepared in example 3 of the present invention;
FIG. 8 is an SEM image of a cellulose acetate nano-micro fiber membrane prepared in comparative example 1 of the present invention;
FIG. 9 is an infrared spectrum of a cellulose acetate nano-micron fiber membrane prepared in comparative example 1 of the present invention;
FIG. 10 is an SEM image of a regenerated cellulose nano-micro fiber membrane prepared in comparative example 2 of the present invention;
FIG. 11 is an IR spectrum of a regenerated cellulose nano-micron fiber membrane prepared in comparative example 2 of the present invention.
Detailed Description
Specific examples of the present invention are given below. The specific examples are only intended to illustrate the invention in further detail and do not limit the scope of protection of the claims of the present application.
The invention provides a preparation method (method for short) of ether bond connected polybasic carboxyl modified regenerated cellulose, which is characterized by comprising the following steps:
preferably, in step 1, the cellulose acetate product is a cellulose acetate film, a cellulose acetate nonwoven fabric, a cellulose acetate fiber or a cellulose acetate resin;
preferably, in step 1, the strongly alkaline solution is a sodium hydroxide solution, a potassium hydroxide solution or a calcium hydroxide solution, preferably a sodium hydroxide solution;
preferably, in step 1, the obtained regenerated cellulose product is washed to be neutral by deionized water;
preferably, in the step 1, the saponification reaction temperature is 20-30 ℃, and the saponification reaction time is 12-24 hours;
preferably, in the step 1, the concentration of the strong alkaline solution is 0.05-0.8 mol/L, preferably 0.1-0.5 mol/L;
preferably, in step 1, the cellulose acetate membrane exists in the form of a nano-micron fiber membrane, and the preparation process is as follows: the spinning of fiber membranes is carried out by adopting multi-needle electrostatic spinning equipment, the number of needles can be adjusted according to the width of the receiving roller, and the spinning speed can be improved by increasing the number of needles. The cellulose acetate and the mixed solvent form a spinning solution with the mass fraction of the cellulose acetate of 17-21%; the mixed solvent is an N, N-dimethylformamide/acetone system or an N, N-dimethylformamide/dichloroethane system, wherein the volume ratio of the N, N-dimethylformamide to the acetone or dichloroethane is 1.5-3: 1 (preferably 2: 1); the spinning solution forms fibers at a liquid inlet rate of 0.4-0.8 mL/h under the conditions of spinning voltage of 18-25 kV, ambient temperature of 20-30 ℃ and ambient humidity of 50% -90%, a spinning needle head reciprocates along the radial direction of a receiving roller at a horizontal distance of 10-15 cm away from the grounded receiving roller, a cellulose acetate nano-micron fiber membrane can be received on the surface of the roller, and the cellulose acetate nano-micron fiber membrane is dried in vacuum at 50 ℃ for 48 hours for later use.
Step 2, mixing the regenerated cellulose product obtained in the step 1, a solvent and an alkali activator, stirring and activating the regenerated cellulose for 0.5-1.5 h (preferably 1h), adding halogenated diethyl malonate to perform an alkali-catalyzed etherification grafting reaction, so that halogen and hydroxyl perform a grafting reaction, and simultaneously hydrolyzing ester groups of the halogenated diethyl malonate into carboxyl to obtain a primary product;
preferably, in step 2, the solvent is an organic solvent containing an alkane group, preferably isopropanol, acetone, acetonitrile, dichloromethane, cyclohexane or n-hexane, more preferably isopropanol;
preferably, in step 2, the halogenated diethyl malonate is diethyl bromomalonate or diethyl chloromalonate, preferably diethyl bromomalonate;
preferably, in the step 2, the alkali activator adopts a strong alkaline solution with the mass fraction of 20-30% (preferably 25%); the strong alkaline solution is a sodium hydroxide solution, a potassium hydroxide solution or a calcium hydroxide solution, preferably a sodium hydroxide solution;
preferably, in the step 2, the ratio of the mass of the regenerated cellulose product to the volume of the solvent is 1g:200 ml-600 ml (preferably 1g:400 ml); the molar ratio of the regenerated cellulose product to the solute of the alkali activator is 1: 3-50; the molar ratio of the regenerated cellulose product to the halogenated diethyl malonate is 1: 1-3.
Preferably, in the step 2, the alkali activator is added in a dropwise manner, and stirring and activating are carried out for 0.5-1.5 h after dropwise addition is finished.
Preferably, in step 2, the halogenated diethyl malonate is dissolved in the solvent and then added into the reaction system.
Preferably, in the step 2, the etherification grafting reaction is carried out for 2-12 hours under the stirring condition, and the reaction temperature is 20-70 ℃.
Step 3, washing the primary product obtained in the step 2 by using an ethanol/deionized water mixed solution to remove unreacted substances and micromolecular byproducts, completing the purification of the primary product, and then soaking the primary product in a dilute acid solution until carboxylate is completely converted into carboxyl, so as to obtain an ether bond-connected polybasic carboxyl modified regenerated cellulose product;
preferably, in the step 3, the volume ratio of the ethanol to the deionized water in the ethanol/deionized water mixed solution is 3-1: 1, the washing times are 3-5 times, and 3-5 min is carried out for each time;
preferably, in step 3, the diluted acid solution is protonic acid with a pH of 1-6 (preferably 2-4), preferably hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid or nitric acid;
preferably, in the step 3, the carboxylic acid salt is immersed in the dilute acid solution for 3 to 5 times, the immersion temperature is 20 to 30 ℃, and the immersion time is 10 to 15min each time, so as to ensure that the carboxylic acid salt is completely converted into carboxyl.
Preferably, in step 3, the ether-linked polycarboxy-modified regenerated cellulose product may be washed to neutrality with deionized water.
The method for testing the morphology and the structure of the nano-micron fiber membrane comprises the following steps:
1. and (3) morphology testing: and observing the product morphology structure by using a Scanning Electron Microscope (SEM) to obtain an SEM picture with the magnification of 2000 multiplied by 2000.
2. And (3) testing the structure: scanning the product by a Fourier transform infrared spectrometer (FTIR), wherein the scanning range is 4000-500 cm -1 Scanning precision of 2cm -1 Each sample was scanned 16 times.
3. Testing the adsorptivity of heavy metal ions: (1) preparing Cu with different concentration gradients by a dilution constant volume method 2+ And (3) performing full spectrum scanning on the standard solution by using an ultraviolet-visible spectrophotometer, recording an absorbance (Abs) value under the condition of the maximum absorption wavelength (861.5nm), and performing linear fitting on the concentration and the absorbance value to obtain a corresponding fitting equation. (2) Preparing Cu with a certain volume and a concentration of 200mg/L 2+ Adding the products into the solution respectively, performing vibration adsorption at 25 deg.C and 100rpm, sampling at certain time intervals, measuring absorbance (Abs) value until balance, and calculating corresponding Cu based on fitting equation 2+ Real-time concentration and corresponding adsorption capacity.
Example 1
(1) Spinning a cellulose acetate nano-micron fiber membrane: spinning a fiber membrane by adopting multi-needle electrostatic spinning equipment, wherein the mass fraction of cellulose acetate in a spinning solution is 19 percent, and the cellulose acetate is dissolved in an N, N-dimethylformamide/acetone mixed solvent with the volume ratio of 2: 1; forming fibers by the spinning solution at a liquid inlet speed of 0.6mL/h under the conditions of 20kV spinning voltage, 25 ℃ and 70% environmental humidity, enabling a spinning needle head to reciprocate along the radial direction of a receiving roller at a horizontal distance of 10cm away from the grounded receiving roller, receiving a cellulose acetate nano-micron fiber membrane on the surface of the roller, and performing vacuum drying at 50 ℃ for 48 hours for later use;
(2) preparing a regenerated cellulose nano-micron fiber membrane: soaking 0.25g of dry cellulose acetate nano-micron fiber membrane into 100ml of sodium hydroxide aqueous solution with the concentration of 0.5mol/L, performing saponification reaction for 12 hours under the stirring condition, obtaining a regenerated cellulose nano-micron fiber membrane after the reaction is finished, and then washing the regenerated cellulose nano-micron fiber membrane to be neutral by deionized water;
(3) the regenerated cellulose nano-micron fiber membrane is subjected to etherification, grafting and modification reaction to obtain an initial product: 0.15g of regenerated cellulose nano-micron fiber membrane is immersed in 60ml of isopropanol, so that the ratio of the mass of the regenerated cellulose nano-micron fiber membrane to the volume of the isopropanol is 1g:400 ml; dripping 21.6g of 25% sodium hydroxide aqueous solution under the stirring condition to ensure that the molar ratio of the regenerated cellulose nano-micron fiber membrane to the sodium hydroxide is 1:45, and continuously stirring for 1 h; adding a diethyl bromomalonate (4.0g, 92% purity) solution dissolved in 10ml of isopropanol at the temperature of 60 ℃, wherein the molar ratio of the regenerated cellulose nano-micron fiber membrane to the diethyl bromomalonate is 1:3, and carrying out etherification grafting reaction for 2 hours under the stirring condition;
(4) and washing the primary product with an ethanol/water mixed solution for 3 times, each time for 5min, then soaking the primary product in a dilute hydrochloric acid solution with the pH value of 4 for 3 times, each time for 10min, washing the primary product with deionized water to be neutral, and drying the primary product to obtain the ether bond connected multi-carboxyl modified regenerated cellulose nano-micron fiber membrane.
As can be seen from FIG. 2, the fiber structure of the membrane after the saponification reaction and the 2-hour etherification graft modification reaction was not damaged.
As can be seen from FIG. 3, the IR spectrum was 1730cm -1 A new characteristic absorption peak appears at (-COOH), which shows that the alkali-catalyzed etherification reaction is successfully completed on the surface of the regenerated cellulose nano-micron fiber film, and the polybasic carboxyl is introduced into the regenerated cellulose.
Heavy metal ion adsorption test, ether bond connected poly-carboxyl modified regenerated cellulose nano-micron fiber membrane to Cu 2+ The adsorption of (2) reaches the adsorption equilibrium after 1.5h, and the maximum adsorption quantity is 40.0 mg/g.
Example 2
Steps (1), (2) and (4) of this example were the same as steps (1), (2) and (4) of example 1, respectively, and the etherification grafting reaction time of step (3) was 3 hours.
As can be seen from FIG. 4, the fiber structure of the membrane after the saponification reaction and the 3-hour etherification graft modification reaction was not damaged.
As can be seen from FIG. 5, the IR spectrum was 1730cm -1 A new characteristic absorption peak appears at (-COOH), which shows that the alkali-catalyzed etherification reaction is successfully completed on the surface of the regenerated cellulose nano-micron fiber film, and the polybasic carboxyl is introduced into the regenerated cellulose.
Heavy metal ion adsorption test, ether bond connected poly-carboxyl modified regenerated cellulose nano-micron fiber membrane to Cu 2+ The adsorption of (2) can reach the adsorption equilibrium after 2.0h, and the maximum adsorption quantity is 66.7 mg/g.
Example 3
Steps (1), (2) and (4) of this example were the same as steps (1), (2) and (4) of example 1, respectively, and the etherification grafting reaction time of step (3) was 4 hours.
As can be seen from FIG. 6, the fiber structure of the membrane after the saponification reaction and the 4-hour etherification graft modification reaction was not damaged.
As can be seen from FIG. 7, the IR spectrum was 1730cm -1 A new characteristic absorption peak appears at (-COOH), which shows that the alkali-catalyzed etherification reaction is successfully completed on the surface of the regenerated cellulose nano-micron fiber film, and the polybasic carboxyl is introduced into the regenerated cellulose.
Heavy metal ion adsorption test, ether bond connected poly-carboxyl modified regenerated cellulose nano-micron fiber membrane to Cu 2+ The adsorption of (2) can reach the adsorption equilibrium after 2.0h, and the maximum adsorption quantity is 86.7 mg/g.
Comparative example 1
This comparative example obtained a cellulose acetate nanofiber membrane using only step (1) of example 1.
As can be seen from FIG. 8, the average fiber diameter of the cellulose acetate nano-micro fiber membrane was about 2.6. mu.m.
As can be seen from FIG. 9, the diameters are 1218cm respectively -1 (C-O)、1362cm -1 (C-CH 3 )、1735cm -1 (C＝O)、3461cm -1 The characteristic absorption peak is shown at (-OH).
Heavy metal ion adsorption test, cellulose acetate nano-micron fiber membrane to Cu 2+ The adsorption of (1) can reach the adsorption equilibrium after 1.0h, and the maximum adsorption quantity is 23.3 mg/g.
Comparative example 2
This comparative example obtained a regenerated cellulose nano-micro fiber membrane using only step (1) and step (2) of example 1.
As can be seen from FIG. 10, the fiber structure of the regenerated cellulose nano-micro fiber membrane was not damaged after the saponification reaction.
As can be seen from FIG. 11, it is at 1362cm -1 (C-CH 3 ) And 1735cm -1 The characteristic absorption peak at (C ═ O) disappeared at 3461cm -1 The absorption peak is shifted to 3330cm in the low wave number direction -1 Indicating that the ester groups in the cellulose acetate were completely hydrolyzed.
Heavy metal ion adsorption test, regenerated cellulose nano-micron fiber membrane to Cu 2+ The adsorption of (2) can reach the adsorption equilibrium at 0.5h, and the maximum adsorption quantity is 10.0 mg/g.
The invention is applicable to the prior art where nothing is said.
Claims (10)
1. A method for preparing ether linkage connected polybasic carboxyl modified regenerated cellulose, which is characterized by comprising the following steps:
step 1, adding a cellulose acetate product into an excessive strong alkaline solution, and performing saponification to change ester groups of the cellulose acetate into hydroxyl groups to obtain a regenerated cellulose product;
the cellulose acetate product is a cellulose acetate film, a cellulose acetate non-woven fabric, cellulose acetate fibers or cellulose acetate resin;
step 2, mixing the regenerated cellulose product obtained in the step 1, a solvent and an alkali activator, activating the regenerated cellulose, adding halogenated diethyl malonate to perform an alkali-catalyzed etherification grafting reaction to enable halogen and hydroxyl to perform a grafting reaction and ester groups of the halogenated diethyl malonate to be hydrolyzed into carboxyl groups, and obtaining an initial product;
and 3, washing the primary product obtained in the step 2 to remove unreacted substances and micromolecular byproducts, thereby completing the purification of the primary product, and then soaking the primary product in a dilute acid solution until the carboxylate is completely converted into carboxyl, thereby obtaining the ether bond-linked polybasic carboxyl modified regenerated cellulose product.
2. The method for preparing ether linkage multi-carboxyl modified regenerated cellulose according to claim 1, wherein the cellulose acetate membrane is in the form of a nano-micron fiber membrane in step 1, and the preparation process is as follows: spinning a fiber membrane by adopting multi-needle electrostatic spinning equipment; the cellulose acetate and the mixed solvent form a spinning solution with the mass fraction of the cellulose acetate of 17-21%; the mixed solvent is an N, N-dimethylformamide/acetone system or an N, N-dimethylformamide/dichloroethane system, wherein the volume ratio of the N, N-dimethylformamide to the acetone or dichloroethane is 1.5-3: 1; the spinning solution forms fibers at a liquid inlet speed of 0.4-0.8 mL/h under the conditions of spinning voltage of 18-25 kV, ambient temperature of 20-30 ℃ and ambient humidity of 50% -90%, a spinning needle head makes reciprocating motion along the radial direction of a receiving roller at a horizontal distance of 10-15 cm from the grounded receiving roller, and a cellulose acetate nano-micron fiber membrane is received on the surface of the roller.
3. The method for preparing ether linkage-connected polycarboxy modified regenerated cellulose according to claim 1, wherein in step 1, the strongly alkaline solution is a sodium hydroxide solution, a potassium hydroxide solution or a calcium hydroxide solution, and the concentration is 0.05 to 0.8 mol/L.
4. The method for producing ether-linked polycarboxy-modified regenerated cellulose according to claim 1, wherein the saponification reaction is carried out at 20 to 30 ℃ for 12 to 24 hours in step 1 under stirring.
5. The method for producing an ether-linked polycarboxy-modified regenerated cellulose according to claim 1, wherein in the step 2, the solvent is an organic solvent containing an alkane group; the halogenated diethyl malonate is bromo-diethyl malonate or chloro-diethyl malonate; the alkali activator adopts 20-30% of sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution by mass fraction.
6. The method for producing ether-linked polycarboxy-modified regenerated cellulose according to claim 1, wherein in the step 2, the mass ratio of the regenerated cellulose product to the volume of the solvent is 1g:200ml to 600 ml; the molar ratio of the regenerated cellulose product to the solute of the alkali activator is 1: 3-50; the molar ratio of the regenerated cellulose product to the halogenated diethyl malonate is 1: 1-3.
7. The method for producing ether-bond-linked polycarboxy-modified regenerated cellulose according to claim 1, wherein the conditions for activating the regenerated cellulose in step 2 are: activating for 0.5-1.5 h under the stirring condition; the etherification grafting reaction is carried out for 2-12 h under the stirring condition, and the reaction temperature is 20-70 ℃.
8. The method for preparing ether linkage-connected polycarboxyl-modified regenerated cellulose as claimed in claim 1, wherein in step 3, a mixed solution of ethanol and deionized water is used for washing, wherein the volume ratio of ethanol to deionized water is 3-1: 1, the number of washing times is 3-5, and each washing time is 3-5 min.
9. The method for producing an ether-linked polycarboxy-modified regenerated cellulose according to claim 1, wherein the diluted acid solution in step 3 is a protonic acid having a pH of 1 to 6.
10. The method for preparing ether linkage-connected polycarboxyl-modified regenerated cellulose as claimed in claim 1, wherein in step 3, the cellulose is immersed in a dilute acid solution for 3 to 5 times at a temperature of 20 to 30 ℃ for 10 to 15min each time.
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